Classifications

• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
  • C09J123/26—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers modified by chemical after-treatment
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
  • B32B37/12—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by using adhesives
  • B32B37/1207—Heat-activated adhesive
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
  • B32B7/04—Interconnection of layers
  • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F8/00—Chemical modification by after-treatment
  • C08F8/42—Introducing metal atoms or metal-containing groups
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J5/00—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers
  • C09J5/06—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers involving heating of the applied adhesive
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
  • B32B37/12—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by using adhesives
  • B32B37/1207—Heat-activated adhesive
  • B32B2037/1215—Hot-melt adhesive
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/54—Silicon-containing compounds
  • C08K5/541—Silicon-containing compounds containing oxygen
  • C08K5/5415—Silicon-containing compounds containing oxygen containing at least one Si—O bond
  • C08K5/5419—Silicon-containing compounds containing oxygen containing at least one Si—O bond containing at least one Si—C bond
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2314/00—Polymer mixtures characterised by way of preparation
  • C08L2314/06—Metallocene or single site catalysts
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L57/00—Compositions of unspecified polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • C08L57/02—Copolymers of mineral oil hydrocarbons
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J2400/00—Presence of inorganic and organic materials
  • C09J2400/20—Presence of organic materials
  • C09J2400/26—Presence of textile or fabric
  • C09J2400/263—Presence of textile or fabric in the substrate
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J2423/00—Presence of polyolefin
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J2423/00—Presence of polyolefin
  • C09J2423/10—Presence of homo or copolymers of propene
  • C09J2423/106—Presence of homo or copolymers of propene in the substrate
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J2451/00—Presence of graft polymer
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T156/00—Adhesive bonding and miscellaneous chemical manufacture
  • Y10T156/10—Methods of surface bonding and/or assembly therefor
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/249921—Web or sheet containing structurally defined element or component
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/249921—Web or sheet containing structurally defined element or component
  • Y10T428/249953—Composite having voids in a component [e.g., porous, cellular, etc.]
  • Y10T428/249982—With component specified as adhesive or bonding agent
  • Y10T428/249985—Composition of adhesive or bonding component specified
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/31504—Composite [nonstructural laminate]
  • Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
  • Y10T428/31573—Next to addition polymer of ethylenically unsaturated monomer
  • Y10T428/31587—Hydrocarbon polymer [polyethylene, polybutadiene, etc.]
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/31504—Composite [nonstructural laminate]
  • Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
  • Y10T428/31609—Particulate metal or metal compound-containing
  • Y10T428/31612—As silicone, silane or siloxane
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/31504—Composite [nonstructural laminate]
  • Y10T428/31652—Of asbestos
  • Y10T428/31663—As siloxane, silicone or silane

Definitions

• Hot-melt adhesives for use as lamination adhesives have been known for a long time.
• the problem frequently is that these adhesives have a short open time leading to excessively rapid cooling of the applied adhesive and in the process to its solidification.
• the adhesive is no longer able to wet the surface of the joining partner, so that an adhesive bond can no longer form.
• This effect is a problem particularly in the case of hot-melt adhesives that are based on amorphous thermoplastic polymers.
• An additional disadvantage of this type of hot-melt adhesives is that the adhesives remain thermoplastic even after the application. When heating an adhesive bond based on such adhesives, the adhesive consequently can melt again and the bond can be destroyed when exposed to a load.
• thermoplastic hot-melt adhesives are very hard (i.e., not bendable or flexible) in the cured state, which is in conflict with their use for textile laminations, particularly in the clothing sector.
• the user wants a “soft touch,” i.e., to the extent possible the adhesive should not be perceivable.
• polyolefin-based hot-melt adhesives in particular require high melting temperatures, so that such adhesives are not suitable for heat-sensitive materials, such as, for example, thin polyurethane membranes in the textile sector.
• heat-sensitive materials such as, for example, thin polyurethane membranes in the textile sector.
• Reactive polyurethane hot-melt adhesives therefore have a long open time, particularly if they are applied in thin layers, but only a low initial strength. Moreover, such adhesives frequently have residual monomeric isocyanate contents of more than 1%, so that they have to be labeled R40 (suspected carcinogenic effect) according to the current labeling regulations.
• An additional class of reactive hot-melt adhesives is based on silane-grafted poly- ⁇ -olefins, as described in U.S. Pat. No. 5,994,474 or DE 40 00 695 A1, for example. These hot-melt adhesives achieve a very high strength with high heat stability and they also have a very high initial strength.
• WO 2004/081138 A1 describes hot-melt adhesives based on silane functional poly- ⁇ -olefins that are combined with tackifiers and thermoplastic elastomers.
• the tackifiers in the compositions according to WO 2004/081138 have softening points of more than 60° C.
• the corresponding adhesives are described as advantageous sealing materials in window construction or the bonding of several glass layers.
• moisture-curing adhesive systems based on silane functional poly- ⁇ -olefin polymers, thermoplastic components having a softening point above 120° C., silane-based tackiness improving agents as well as thermoplastic tackifying resins having a softening point above 80° C. These adhesives were used for the construction of solar modules, particularly for sealing and suspension frames of solar modules.
• WO 2009/023553 A1 describes hot-melt adhesives based on silane functional polymers that are liquid at room temperature as well as silane functional polymers that can contain in addition silane-based adhesion tackiness improving agents.
• Silane functional polymers that are preferred in the context of this disclosure are acrylate modified polyethers that are liquid at room temperature and are reacted, for example, with acrylate copolymers that contain free carboxy groups.
• the disadvantage of this compound is that, during the curing of the adhesive, it is also not incorporated in the developing network and can be released from the adhesive over time.
• the additional soft resin therefore has to be added in relatively large quantities in the range from 20 to 40 wt %.
• a hot-melt composition which comprises a) at least one thermoplastic poly- ⁇ -olefin (P) that is solid at 25° C. and that contains silane groups, b) at least one soft resin (SR) having a melting point or softening point between ⁇ 10° C. and 40° C.; and c) at least one silane that is liquid at 25° C.
• P thermoplastic poly- ⁇ -olefin
• SR soft resin
• the hot-melt composition according to the invention is associated, on the one hand, with a reduction of the viscosity before the processing, and, on the other hand, with a longer open time.
• the liquid silane is incorporated in the polymer network during the curing of the composition and therefore it cannot escape from the adhesive bond over the lifespan of a manufactured product.
• the adhesive-melt composition according to the invention has the same advantageous properties as compositions without the silane that is liquid at 25° C., i.e., they have a broad adhesion spectrum and result in bonding capable of withstanding high loads and are exceedingly heat stable. In the case of adhesive bonds that are composed of such hot-melt adhesive compositions, a highly reduced creep behavior can be observed.
• hot-melt adhesive compositions according to the invention are highly advantageous with regard to their aspects pertaining to occupational hygiene and safety.
• a further aspect of the present invention is a composite comprising a first substrate, a second substrate as well as a layer of a hot-melt adhesive composition according to the invention applied in between, as well as a method for manufacturing such a composite.
• the present invention relates to a hot-melt adhesive composition
• a hot-melt adhesive composition comprising a) at least one thermoplastic poly- ⁇ -olefin (P) that is solid at 25° C. and that contains silane groups, b) at least one soft resin (SR) having a melting point or softening point between ⁇ 10° C. and 40° C.; and c) at least one silane that is liquid at 25° C.
• P thermoplastic poly- ⁇ -olefin
• SR soft resin
• thermoplastic poly- ⁇ -olefin (P) that is solid at 25° C. and that contains silane groups to be a silane-grafted poly- ⁇ -olefin (P).
• the poly- ⁇ -olefin (P) that contains silane groups prefferably has a softening temperature between 70° C. and 150° C., in particular between 80° C. and 120° C., and particularly preferably between 90° C. and 110° C.
• the softening point is measured here using the ring & ball method based on DIN EN 1238.
• Such poly- ⁇ -olefins (P) that contain silane groups are known to the person skilled in the art. They can be produced, for example, by grafting unsaturated silane, such as vinyl trimethoxysilane, to a poly- ⁇ -olefin. A detailed description of the production of silane-grafted poly- ⁇ -olefins can be found in U.S. Pat. No. 5,994,474 and DE 40 00 695 A1, for example.
• a silane-grafted polyethylene or polypropylene is particularly suitable as solid poly- ⁇ -olefin (P) that contains silane groups.
• Additional preferred poly- ⁇ -olefins (P) that contain silane groups are silane-grafted poly- ⁇ -olefins, which are poly- ⁇ -olefins manufactured by means of metallocene catalysts to which silane groups have been grafted.
• silane-grafted polyolefin homopolymers or polypropylene homopolymers are silane-grafted polyolefin homopolymers or polypropylene homopolymers.
• the grafting degree of the silane-grafted poly- ⁇ -olefin (P) is advantageously more than 1 wt %, in particular more than 3 wt % silane, relative to the weight of the polyolefin. If a silane-grafted poly- ⁇ -olefin (P) produced according to the Ziegler-Natta method is used as silane-grafted poly- ⁇ -olefin (P), then the grafting degree is preferably between 1 and 8 wt %, in particular between 1.5 and 5 wt %. If poly- ⁇ -olefins produced using metallocene catalysts are used as the silane-grafted poly- ⁇ -olefin, the grafting degree is preferably between 8 and 12 wt %.
• the hot-melt adhesive composition according to the invention has at least two different poly- ⁇ -olefins (P) that contain silane groups.
• P poly- ⁇ -olefins
• the combination of silane-grafted poly- ⁇ -olefins that can be obtained by the Ziegler-Natta method and of silane-grafted polypropylene homopolymers that can be obtained by the metallocene catalyst method is particularly preferable.
• the content of all the poly- ⁇ -olefins (P) that contain silane groups in the hot-melt adhesive composition is more than 40 wt %, and in particular it is between 45 and 75 wt %.
• the hot-melt adhesive composition according to the invention moreover contains at least one soft resin (SR) having a melting point or softening point between ⁇ 10° C. and 40° C., preferably between 0° C. and 25° C., and in particular between 10° C. and 25° C. Due to the fact that the soft resin (SR) at room temperature (25° C.) is very close to the melting or softening point, it is either already liquid or very soft at room temperature.
• the soft resin can be a natural resin or a synthetic resin.
• soft resins are resins having a medium to high molecular weight from the classes of the paraffin resins, hydrocarbon resins, polyolefins, polyesters, polyethers, polyacrylates or amino resins.
• the soft resin (SR) is a hydrocarbon resin, in particular an aliphatic C 5 -C 9 hydrocarbon resin.
• An aliphatic C 5 hydrocarbon resin that is commercially marketed under the trade name Wingtack® 10 by the company Cray Valley is particularly suitable as soft resin (SR).
• Additional soft resins are, for example, polyterpene resins that are commercially marketed, for example, as Sylvares® TR A25 by Arizona Chemical, USA, and rosin esters and tall oil resin esters that are commercially marketed, for example, as Sylvatac® RE 12, Sylvatac® RE 10, Sylvatac° RE 15, Sylvatac RE 20, Sylvatac® RE 25 or Sylvatac® RE 40 by Arizona Chemical, USA.
• polyterpene resins that are commercially marketed, for example, as Sylvares® TR A25 by Arizona Chemical, USA
• rosin esters and tall oil resin esters that are commercially marketed, for example, as Sylvatac® RE 12, Sylvatac® RE 10, Sylvatac° RE 15, Sylvatac RE 20, Sylvatac® RE 25 or Sylvatac® RE 40 by Arizona Chemical, USA.
• EscorezTM 5040 Exxon Mobil Chemical
• Hydrocarbon resins that are suitable as soft resins are, for example, Picco A10 (Eastman Kodak) and Regalite R1010 (Eastman Kodak).
• the content of the soft resin component (SR) is preferably approximately 5 to 35 wt %, in particular approximately 15 to 25 wt %, relative to the total weight of the hot-melt adhesive composition.
• the weight ratio of the soft resin component (SR) to the component consisting of poly- ⁇ -olefins (P) that contain silane groups is less than 0.5.
• the weight ratio is preferably in the range of approximately 0.2 to 0.4, and particularly preferably in the range of approximately 0.3 to 0.4.
• the silane that is liquid at 25° C. comprises silane compounds in which the silane contains at least one silyl alkoxy functionality.
• siloxane groups hydrolyze first, releasing alcohols to form silanols which, with splitting off of water, can react with additional silanol groups in the hot-melt adhesive composition.
• silanol groups are also formed inter alia during the hydrolysis of the silane groups in the poly- ⁇ -olefin that contains silane groups, so that the silane that is liquid at room temperature is bound covalently to the poly- ⁇ -olefin that contains silane groups, in the hardened composition.
• the silane that is liquid at 25° C. preferably has at least two alkoxy functionalities bound to silicon, since, as a result, it is possible to increase the crosslinking in the resulting completely cured hot-melt adhesive composition.
• the silane that is liquid at 25° C. has three alkoxy functionalities bound to silicon, which results in a particularly effective crosslinking and a high initial strength of the adhesive.
• the silane that is liquid at 25° C. is an alkyltrialkoxysilane, in which the alkyl group preferably has 6 to 24 carbon atoms and each alkoxy group preferably has 1 to 5 carbon atoms.
• the silane that is liquid at 25° C. is hexadecyltrimethoxysilane.
• the silane that is liquid at 25° C. preferably also has as high as possible a boiling temperature, so that it is not released during the heating of the hot-melt adhesive into the environment.
• the boiling temperature of the silane is preferably at least 130° C., particularly preferably at least 150° C., and in particular at least 180° C.
• the weight proportion of the silane that is liquid at 25° C. is preferably approximately 3 to 20 wt %, in particular approximately 5 to 15 wt %, and particularly preferably approximately 6 to 12 wt %, relative to the total weight of the hot-melt adhesive composition.
• the hot-melt adhesive composition according to the invention can contain, in addition to the poly- ⁇ -olefin (P) that contains silane groups, an additional thermoplastic poly- ⁇ -olefin (P′) that is solid at 25° C.
• This polymer can be a homopolymer or copolymer of unsaturated monomers, in particular from the group comprising ethylene, propylene, butylene, isobutylene, isoprene, vinyl acetate or vinyl esters with C3 to C12 carboxylic acids and (meth)acrylate.
• EVA Ethylene vinyl acetate
• APAO atactic poly- ⁇ -olefins
• APAO amorphous poly- ⁇ -olefin
• polypropylene and polyethylene are particularly preferable.
• Atactic poly- ⁇ -olefins are quite particularly preferable.
• the solid thermoplastic polymers (P′) preferably have a softening point of more than 90° C., in particular between approximately 90 and 130° C.
• the molecular weight Mn is preferably between approximately 7000 and 250,000 g/mol.
• the weight ratio of the solid poly- ⁇ -olefins (P) that contain silane groups to the solid thermoplastic polymer component (P′) is particularly preferably in the range from 1:1 to 20:1.
• the hot-melt adhesive composition according to the invention moreover contains preferably at least one catalyst which catalyzes the reaction of silane groups, in particular a phosphoric acid ester or an organotin compound, preferably dibutyltin laurate (DBTL).
• the catalyst is advantageously contained in a quantity of more than 0.05 wt %, in particular in a quantity in the range from approximately 0.1 to 1 wt %, in the hot-melt adhesive composition.
• hot-melt adhesive compositions according to the invention can contain additional auxiliary substances and additives, particularly those selected from the group comprising plasticisers, adhesive promoters, UV absorption agents, UV and heat stabilizers, optical brighteners, fungicides, pigments, dyes, fillers and desiccants.
• thermoplastic poly- ⁇ -olefins (P) that are solid at 25° C. and that contain silane groups and all the soft resins (SR) and all the optionally present solid thermoplastic polymers (P′) to be more than approximately 80 wt %, preferably more than approximately 90 wt %, of the hot-melt adhesive composition.
• hot-melt adhesive compositions that consist substantially of a thermoplastic poly- ⁇ -olefin (P) that is solid at 25° C. and that contains silane groups, soft resin (SR), at least one silane that is liquid at 25° C., optionally solid thermoplastic polymer (P′), as well as a catalyst that catalyzes the reaction of silane groups.
• P thermoplastic poly- ⁇ -olefin
• SR soft resin
• P′ optionally solid thermoplastic polymer
• the silane groups in the poly- ⁇ -olefin (P) that contains silane groups as well as in the silane that is liquid at 25° C. react in contact with water to form silanol groups, which subsequently react with other silanol groups with splitting off of water to form siloxane groups (—Si—O—Si—) and produce a crosslinking of the hot-melt adhesive compositions. Therefore, it is advantageous to use, for the production of the hot-melt adhesive composition according to the invention, raw materials that are dried as well as possible, and that protect the adhesives during production, storage and application to the extent possible from contact with water or atmospheric moisture.
• the addition of silanes that are liquid at 25° C. improves the sensitivity of the adhesive to water, since, as a result of the reaction of the silane with water, at first no crosslinking of the poly- ⁇ -olefin that contains silane groups occurs.
• the hot-melt adhesive compositions according to the invention are liquefied by melting the thermoplastic ingredients.
• the viscosity of the hot-melt adhesive compositions should be adapted to the application temperature.
• the application temperature at which the adhesive is in a form that can be processed easily is in the range from 90 to 200° C. In this temperature range, the viscosity is approximately 1500 to 50,000 mPa ⁇ s. If the viscosity is substantially higher, then the application is difficult, whereas, if the viscosity is substantially lower than 1500 mPa ⁇ s, the adhesive becomes so highly fluid that it runs off the material surface to be glued at the time of the application, before solidifying due to cooling.
• a particular advantage of the hot-melt adhesive composition according to the invention is that, even at low application temperatures, it has a sufficient viscosity that allows application.
• the setting and solidification of the hot-melt adhesive that occurs during the cooling results in a rapid build up of strength and a high early adhesive strength of an adhesive bond.
• care must be taken therefore to ensure that the gluing occurs within the time period in which the adhesive has not yet cooled excessively, i.e., the gluing must occur while the adhesive is still liquid or at least still tacky and deformable.
• the hot-melt adhesive composition will continue to crosslink and it will gain mechanical strength—within a time period of typically several hours or days —even after cooling, due to the influence of water, particularly atmospheric moisture.
• the reactive hot-melt adhesive compositions cannot be heated reversibly and liquefy again as a result.
• the use of such hot-melt adhesive compositions is advantageous particularly for uses in which the glued composite is exposed to high temperatures during the course of its utilization or lifespan, since the gluing at such temperatures does not incur any damage at such temperatures.
• the use of such hot-melt adhesives is also advantageous in that they undergo significantly less creep due to the crosslinking.
• An additional aspect of the invention relates to a composite, comprising a first substrate (S1), which comprises glass, plastic, wood, film, foam or a textile, preferably a textile, a hot-melt adhesive composition as described above, or a hot-melt adhesive composition crosslinked due to the influence of water as described above, as well as a second substrate (S2), wherein the hot-melt adhesive composition or the crosslinked hot-melt adhesive composition is arranged between the first substrate (S1) and the second substrate (S2).
• a first substrate (S1) which comprises glass, plastic, wood, film, foam or a textile, preferably a textile, a hot-melt adhesive composition as described above, or a hot-melt adhesive composition crosslinked due to the influence of water as described above, as well as a second substrate (S2), wherein the hot-melt adhesive composition or the crosslinked hot-melt adhesive composition is arranged between the first substrate (S1) and the second substrate (S2).
• film denotes in particular bendable flat films made of polyolefins at a thickness of 0.05 mm to 5 mm, which can be rolled up.
• sealing webs are also used, as are typically used for sealing tunnels, roofs or swimming pools, in a thickness of typically 1 to 3 mm, and in special cases even in a thickness up to a maximum of 5 mm.
• Such polyolefin films are usually manufactured by spreading, pouring, calendaring or extrusion, and they are typically available commercially in rolls or manufactured on site. They can have a single-layer or multilayer structure.
• polyolefin films can contain additional additives and processing agents, such as fillers, UV and heat stabilizers, plasticisers, anti-friction agents, biocides or flame retardants, antioxidants, pigments such as titanium dioxide or carbon black, for example, and dyes.
• additional additives and processing agents such as fillers, UV and heat stabilizers, plasticisers, anti-friction agents, biocides or flame retardants, antioxidants, pigments such as titanium dioxide or carbon black, for example, and dyes.
• the second substrate (S2) can be of various types.
• the substrates can be made, for example, from plastic, in particular polyolefin or ABS, metal, painted metal, wood, wood materials, glass or fiber materials.
• the substrate is preferably a shaped solid.
• the second substrate (S2) is a fiber material, in particular a natural fiber material.
• the second substrate it is preferable for the second substrate to be a polyurethane, in particular a polyurethane membrane.
• the second substrate (S2) is a polypropylene.
• the surface of the second substrate (S2) can be subjected to a preliminary treatment, thus, in particular, by cleaning or by applying a primer. However, it is preferable not to apply a primer to the second substrate.
• the described composite is preferably an industrially manufactured article, in particular a textile article.
• the article can also be a glass article, in particular for automobile applications.
• the high content of silane ensures a permanent gluing.
• the article is a sandwich element, in particular for the construction or mobile home sector.
• sandwich elements as a rule consist of several layers made of plastics, such as, for example, ABS or PVC, a foam, such as XPS or EPS, or of wood layers.
• An additional aspect of the present invention covers a method for producing a composite material, as described above.
• This method comprises the steps of (i) melting the hot-melt adhesive composition according to the invention as described above, (ii) applying the molten hot-melt adhesive composition to a first substrate (S1) which comprises glass, plastic or wood, a film, a foam or a textile, preferably a textile, (iii) optionally heating the first substrate (S1), and (iv) putting the second substrate (S2), preferably a polyurethane membrane, in contact with the applied molten hot-melt adhesive composition.
• a first substrate which comprises glass, plastic or wood, a film, a foam or a textile, preferably a textile
• S2 preferably a polyurethane membrane
• Heating the film (S1) makes the film soft and able to adapt to the geometry of the carrier, without any folds forming.
• the polyolefin films used here can be decorative films that have a surface structure. This surface structure can be imprinted, for example, before, during or after gluing.
• the contacting step occurs in particular with a contact pressure in particular between 0.1 bar and 1 bar, preferably of at least 0.8 bar (corresponding to the application of a vacuum of up to 0.9 bar, particularly of at least 0.2 bar).
• the contact pressure is generated preferably by applying a negative pressure in the space between the second substrate (S2) and the polyolefin film (S1).
• the above-mentioned contact pressure therefore is generated in particular by the application of a negative pressure of up to 0.9 bar, preferably of at least 0.2 bar.
• the application of a negative pressure is not necessary, since here the coated substrate and the substrate to be laminated are preferably compressed together using a calendering roll.
• the contacting step occurs preferably at a hot-melt adhesive temperature of 50° C. or more, in particular at a temperature between approximately 50 and 200° C., particularly preferably between approximately 90 and 120° C.
• the molten hot-melt adhesive composition is applied either on the carrier and/or the surface of the foam or textile.
• the gluing of the carrier to the foam or textile occurs in any case under the influence of heat by joining and pressing.
• the hot-melt adhesive composition according to the invention is characterized, on the one hand, by the absence of isocyanates, which entails advantages with regard to occupational hygiene and safety.
• isocyanates which entails advantages with regard to occupational hygiene and safety.
• even at low application temperatures, such as from approximately 100 to 110° C. it has a viscosity that is suitable for application, which allows its use in particular for gluing heat-sensitive substances, such as polyurethane membranes, for example.
• the hot-melt adhesive composition according to the invention in spite of having on average a lower content of soft resin in comparison to EP 2 113 545, has a longer open time, which makes it unnecessary to use the “reactivation” or remelting of the adhesive, which is commonly required in the prior art, before the joining of the surface of the joining partner. This leads to a greatly simplified gluing process, as a result of which the hot-melt adhesive composition according to the invention is also advantageous financially.
• the hot-melt adhesive composition according to the invention is exceedingly stable during storage and it has special processing properties, particularly in the application temperature range from approximately 0° C. to 130° C. At these temperatures, the hot-melt adhesive composition according to the invention also has a stable viscosity over a longer time.
• the hot-melt adhesive composition according to the invention is moreover odor-free, and even if applied in thick layers it is free of bubbles and can be processed rapidly, and it is characterized by a satisfactory adhesion and a satisfactory resistance to environmental influences, in particular to textile washing processes, for example.
• a hot-melt adhesive composition was prepared, in which the starting substances were mixed in accordance with the weight contents indicated in Table 1 at a temperature of 150° C. and under an inert gas atmosphere in a stirring device.
• Hot-melt adhesive composition 1 P1 49.5 wt % P2 7.6 wt % P3 15.2 wt % Wingtack ® 10 19.0 wt % Hexadecyltrimethoxysilane 8.4 wt % Phosphate ester based on long-chain alcohols 0.33 wt % Open time (sec) 230 sec Viscosity* at 110° C. (Pa ⁇ s) 8500 Viscosity* at 130° C.
• the polymers used can be found in Table 2.
• Density approximately 0.90 g/cm 3 Silane content: approximately 10 wt % (grafting agent: vinyltriethoxysilane) P3 Amorphous poly- ⁇ -olefin (butene-rich) Melt viscosity (170° C.) 6000 to 10,000 cp Density 0.90 g/cm 3 Softening temperature (ring & ball): 114 to 122° C. Tg: ⁇ 27° C.

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• Chemical Kinetics & Catalysis (AREA)
• General Chemical & Material Sciences (AREA)
• Health & Medical Sciences (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Adhesives Or Adhesive Processes (AREA)
• Laminated Bodies (AREA)
• Adhesive Tapes (AREA)

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• 2011
  • 2011-12-19 EP EP20110194299 patent/EP2607442A1/fr not_active Withdrawn
• 2012
  • 2012-12-18 CN CN201280058145.6A patent/CN103958632A/zh active Pending
  • 2012-12-18 EP EP12809769.8A patent/EP2794794B1/fr not_active Not-in-force
  • 2012-12-18 JP JP2014547922A patent/JP2015508427A/ja active Pending
  • 2012-12-18 US US14/357,693 patent/US20140329074A1/en not_active Abandoned
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